WO2003040153A1 - Process for preparing silylorganomercaptans - Google Patents
Process for preparing silylorganomercaptans Download PDFInfo
- Publication number
- WO2003040153A1 WO2003040153A1 PCT/US2002/032608 US0232608W WO03040153A1 WO 2003040153 A1 WO2003040153 A1 WO 2003040153A1 US 0232608 W US0232608 W US 0232608W WO 03040153 A1 WO03040153 A1 WO 03040153A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dioxa
- group
- bis
- tetrathia
- carbon atoms
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Definitions
- This invention relates to the field of processes for preparing organomercaptans. More particularly, the present invention describes a process for preparing organomercaptan by the catalyzed hydrogenolysis of a disulfide, trisulfide, and/or polysulfide.
- U.S. Patent No. 6,147,242 describes a process for preparing 3-mercaptopropyl- triethoxysilane by the homolytic cleavage of the corresponding bis-disulfide.
- the method involves reacting a bis-silylalkylsulfide with an alkali metal and a chlorosilane to provide a silylalkylsulfanylsilane intermediate which is recovered and thereafter hydrolyzed in the presence of refluxing aqueous alcohol to the desired mercaptoalkylsilane.
- the foregoing method is subject to several disadvantages including its use of a chlorosilane which is expensive, the necessity to filter and dispose of hazardous alkali metal salt, and the need to isolate a silylalkylsulfanylsilane intermediate prior to the hydrolysis step.
- Patent EP 649,837 discloses a process for the preparation of methyl mercaptan from the corresponding dimethyl disulfide using a transition metal catalyst which requires a sulfidation pretreatment with a hydrogen sulfide/hydrogen mixture (containing 15 mole percent hydrogen sulfide) at an hourly flow rate of 2 liters mixture per gram of catalyst at 400°C for 4 hours.
- the selectivity and the yield of the process are reported to be improved when the reaction is conducted in the presence of either water or hydrogen sulfide at a concentration of 0.1 to 15 weight percent with respect to the disulfide.
- each R 1 is the same or different alkyl group of up to about 6 carbon atoms, aryl group of up to about 10 carbon atoms or alkoxy group of up to about 6 carbon atoms, or at least two of R and the silicon atom to which they are bonded form a ring system having up to about 12 members and containing no ethylenic unsaturation, and optionally containing at least one heteroatom selected from the group consisting of oxygen, sulfur and nitrogen
- each R 2 is the same or different divalent hydrocarbon group containing no ethylenic unsaturation and having up to about 20 carbon atoms and m is 0 to about 8, with hydrogen under hydrogenolysis conditions in the presence of a catalytically effective amount of Group VIII metal catalyst and in the presence of a catalyst poisoning inhibiting amount of a catalyst poisoning inhibitory agent selected from the group consisting of water, except where the mercaptan product contains at least one hydrolyzable silane group, alkanol of from 1 to about 6 carbon atoms, hydrogen
- the process of this invention does not require presulfiding in order to enhance reactivity or inhibit catalyst poisoning.
- the starting sulfide of the present invention can be chosen from among those of the general formula (I):
- each R 1 is the same or different alkyl group of up to about 6 carbon atoms and preferably of up to 4 carbon atoms, e.g., methyl, ethyl, propyl or butyl; aryl group of up to about 10 carbon atoms such as phenyl or naphthyl; alkoxy group of up to about 6 carbon atoms, and preferably up to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, or isobutoxy; or at least two of R 1 and the silicon atom to which they are bonded form a ring system having up to about 12 ring members with no ethylenic unsaturation and optionally containing one or more oxygen, sulfur and/or nitrogen heteroatom members, e.g., the ring system having the structure each R 2 is a divalent hydrocarbon group containing no ethylenic unsaturation and having up to about 20 carbon atom
- sulfide (I) that can be used for preparing organomercaptans in accordance with the present invention and methods for their manufacture are known in the art and include those disclosed in, e.g., U.S. Patent Nos. 4,072,701 ; 4,408,064; 5,489,701 ;
- Examples of useful disilylalkyldisulfides of formula (I) include bis [3- (triethoxysilyl)propyl] disulfide [56706-10-6], bis[3-(trimethoxysilyl)propyl] disulfide [351 12-
- Examples of useful disilylalkyltrisulfides of formula (I) include bis [3-(triethoxysilyl) propyl] trisulfide [56706-11-7], bis [3-(trimethoxysilyl)pro ⁇ yl] trisulfide [40550-17-2], bis[3- (triisopropoxysilyl)propyl] trisulfide [63501-63-3], 3, 13-dibutyl-3, 13-dimethoxy-2, 14-dioxa-7, 8, 9-trithia-3, 13-disilapentadecane [180003-90-1], 3-(tributoxysilyl)propyl 3-(trimethoxysilyl) propyl trisulfide [89552-63-6], (trithiodi-3, l-propanediyl)bis[tris(cyclopentyloxy)-silane
- Examples of useful disilylalkyltetrasulfides of formula (I) include bis [3- (trimethoxysilyl)propyl] tetrasulfide [41453-78-5], (tetrathiodi-3, 1-propanediyl) bis[tris(isooctyloxy)-silane [180007-08-3], bis[3-triethoxysilyl)propyl] tetrasulfide [40372-72- 3], 4, 4-diethoxy-15, 15-bis (ethoxymethoxy)-3, 16, 18-trioxa-8, 9, 10, 1 l-tetrathia-4, 15- disilaeicosane [167216-77-5], 6, 6, 17, 17-tetrakis(ethoxymethoxy)-3, 5, 18, 20-tetraoxa-10, 11, 12, 13-tetrathia-6, 17-disiladocosane [203457-58-3], 1,
- tetrasulfides are in fact average compositions, including a range from disulfide to octasulfide or higher, and typically are not pure tetrasulfides.
- useful disulfides and trisulfides can be provided as mixtures, the use of which is also contemplated herein.
- the disilylalkyldisulfides are generally preferred due to generation of less by-product H 2 S, with the methoxy and ethoxydisilylpropyldi sulfides being more preferred.
- Hydrogenolysis conditions can include a hydrogen pressure from about 100 psig to about 1000 psig and preferably from about 300 psig to about 600 psig, a temperature of from about 160°C to about 200°C and preferably from about 180°C to about 190°C, a reaction time from about 1 hour to about 5 hours and preferably from about 2 hours to about 3 hours.
- the catalyst employed in the hydrogenolysis reaction is chosen from amongst the Group VIII metals and is preferably selected from the group consisting of nickel, cobalt, rhodium and ruthenium.
- the catalyst is preferably one that is supported on any one of numerous known and conventional catalyst support materials, e.g., diatomaceous earth, carbon, silica, alumina, aluminosilicate, and the like.
- the amount of catalyst employed can vary widely provided of course, it is a catalytically effective amount. In general, catalyst levels of from about 0.1 wt. % to about 10 wt. % and preferably from about 0.5 wt. % to about 1 wt. % based on the weight of sulfide (I) reactant can be employed with good results.
- the catalyst poisoning inhibitory agent of the present can be selected to be water (except where the organomercaptan product contains one or more water sensitive silane groups); an alkanol of from 1 to 6 carbon atoms, preferably selected to match the alkoxy group(s) R 2 of the sulfide (I) reactant, and preferably one selected from the group consisting of methanol, ethanol, butanol and isobutanol; and, hydrogen sulfide.
- Catalyst poisoning inhibitory amounts of the catalyst poisoning inhibitory agent can vary widely and in most cases can be present in the reaction medium at a level of from about 5 wt. % to about 50 wt. % and preferably from about 5 wt. % to about 20 wt. % based on the weight of sulfide (I).
- Comparative Examples 1 -6 illustrate a catalyzed process for making organomercaptan which omits the use of a catalyst poisoning inhibitory agent and as such, are outside the scope of the present invention.
- Examples 1-27 are illustrative of the process for preparing organomercaptan of the present invention and clearly demonstrate the advantage of using a catalyst poisoning inhibitory agent. In the tables of data which accompany all of the examples, the following terms have the designated meanings:
- Polysulfide mixtures of bis[3-(triethoxysilyl)propyl] trisulfide and higher sulfides
- Comparative Example 1 In a 1 liter Hastelloy C autoclave equipped with a mechanical stirrer, cooling coils and a thermocouple, 591.4 grams of mainly bis(3-triethoxysilylypropyl) disulfide were combined with 2.0 grams of a 55 wt % nickel catalyst on a kieselguhr support. After purging the autoclave with nitrogen and then hydrogen, the reactor was pressurized to 620 psig with hydrogen and heated to 190°C while stirring at 1022 rpm. After approximately 180 minutes, the reaction mass was cooled to room temperature and vented to atmospheric pressure. The contents of the reactor were sampled and analyzed by gas ckromatography with the following results:
- Comparative Examples 2-6 Employing substantially the same procedure as described in Comparative Example 1 , additional reactions were carried out with the conditions and results as set forth in Table 2 below.
- Example 2 In a 1 liter Hastelloy C autoclave equipped with a mechanical stirrer, cooling coils and a thermocouple, 310.3 grams of mainly bis(3-triethoxysilylypropyl) disulfide were combined with 5.0 grams of a 55 wt % nickel catalyst on a kieselguhr support. After purging the autoclave with nitrogen and then hydrogen, the reactor was charged with 35 grams of hydrogen sulfide, pressurized to 615 psig with hydrogen and heated to 190°C while stirring at 1087 rpm. After approximately 150 minutes, the reaction mass was cooled to room temperature and vented to atmospheric pressure. The contents of the reactor were sampled and analyzed by gas chromatography with the following results: Table 4
Abstract
A process for preparing an organomercaptan is provided which comprises reacting a sulfide of the general formula (I) in which each R1 is the same or different alkyl group of up to about 6 carbon atoms, aryl group of up to about 10 carbon atoms or alkoxy group of up to about 6 carbon atoms, or at least two of R1 and the silicon atom to which they are bonded form a ring system having up to about 12 ring members with no ethylenic unsaturation and optionally containing one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, each R2 is the same or different divalent hydrocarbon group containing no ethylenic unsaturation and having up to about 20 carbon atoms and m is 0 to about 8, with hydrogen under hydrogenolysis conditions in the presence of a catalytically effective amount of Group VIII metal catalyst and in the presence of a catalyst poisoning inhibiting amount of a catalyst poisoning inhibitory agent selected from the group consisting of water, except where the mercaptan product contains at least one hydrolyzable silane group, alkanol of from 1 to about 6 carbon atoms, hydrogen sulfide and mixtures thereof to provide organomercaptan product of the general formula (II) : (R1)3-Si-R2-SH, in which R?1 and R2¿ each has one of the aforestated meanings.
Description
PROCESS FOR PREPARING SILYLORGANOMERCAPTANS
BACKGROUND OF THE INVENTION
This invention relates to the field of processes for preparing organomercaptans. More particularly, the present invention describes a process for preparing organomercaptan by the catalyzed hydrogenolysis of a disulfide, trisulfide, and/or polysulfide. U.S. Patent No. 6,147,242 describes a process for preparing 3-mercaptopropyl- triethoxysilane by the homolytic cleavage of the corresponding bis-disulfide. The method involves reacting a bis-silylalkylsulfide with an alkali metal and a chlorosilane to provide a silylalkylsulfanylsilane intermediate which is recovered and thereafter hydrolyzed in the presence of refluxing aqueous alcohol to the desired mercaptoalkylsilane. The foregoing method is subject to several disadvantages including its use of a chlorosilane which is expensive, the necessity to filter and dispose of hazardous alkali metal salt, and the need to isolate a silylalkylsulfanylsilane intermediate prior to the hydrolysis step.
Itabashi, CA 54, 2153e (1960), CA, 54, 19466c (1960) and CA, 54, 19466g (1960), describes the reaction of various disulfides with hydrogen over molybdenum (VI) sulfide catalyst at 130°-140°C and 10.7 MPa hydrogen pressure resulting in the hydrogenolysis of the disulfides at the S-S linkage to provide the corresponding organomercaptans in high yields. The high catalyst loading for the reaction (approximately 5 weight percent) and the high cost of the catalyst both add significantly to the expense of this preparative method. A similar process described by Broadbent et al., J Am. Chem. Soc, 16, 1519 (1954), provides thiophenol quantitatively by hydrogenolysis of diphenyl disulfide over Re2S7 in 2-methoxyethanol at 165° to 195°C and 15 MPa hydrogen pressure. At these high temperatures, however, subsequent de- sulfurization exclusively results in the saturated hydrocarbon or aromatic substrate.
In general, precious metal and base metal catalysts have found little application in the selective cleavage of the S-S bond due to the known poisoning effect of the resulting sulfides. In the few cases that have been reported, however, palladium catalysts, which are generally known for their resistance to catalyst poisons, have been the most reactive and have achieved the highest yields. The most striking example of this is the hydrogenolysis of methyl cystine to methyl cysteine in the presence of 25 weight percent of palladium catalyst in aqueous acid at room temperature and atmospheric pressure (Bergmann et. al. Rer. Dtsch. Chem. Ges. 63,987 (1930)). The necessity to use an unusually high loading of expensive palladium catalyst, however, precludes its use in all but a limited number of research applications. Patent EP 649,837 discloses a process for the preparation of methyl mercaptan from the corresponding dimethyl disulfide using a transition metal catalyst which requires a sulfidation pretreatment with a hydrogen sulfide/hydrogen mixture (containing 15 mole percent hydrogen sulfide) at an hourly flow rate of 2 liters mixture per gram of catalyst at 400°C for 4 hours. The selectivity and the yield of the process are reported to be improved when the reaction is conducted in the presence of either water or hydrogen sulfide at a concentration of 0.1 to 15 weight percent with respect to the disulfide.
Other catalyst systems have also been reported that are based on transition metal sulfides since the sulfide phases are believed to be more resistant to poisoning by sulfur-containing molecules (Calais et al. J of Cat., 144, 160-174 (1993)). The use of platinum sulfides (Dutch Patent Application No. 6,402,424) for the reduction of diphenyl disulfide to phenyl mercaptan as well as the sulfides of Raney Ni and Raney Co (French Patent Application No. 2,008,331) and Ru, Rh, Pt, Ir, and Pd (German Patent Application No. DE 1,903,968) require relatively high hydrogen pressures, typically in excess of 5-10 MPa.
SUMMARY OF THE INVENTION In accordance with the present invention, a process is provided for preparing an organomercaptan which comprises reacting a sulfide of the general formula (I)
(R')3-Si-R2-SH (II) in which R1 and R2 each has one of the aforestated meanings.
Unlike the catalyst sulfidation pretreatment required by the process described in EP 649,837, supra, the process of this invention does not require presulfiding in order to enhance reactivity or inhibit catalyst poisoning.
Under normal conditions, most base metals and precious metal catalysts are poisoned by the formation of sulfides and particularly by alkyl mercaptans. However, it has been discovered
that when hydrogenolysis of sulfide is conducted in the presence of a catalyst poisoning inhibitory agent in accordance with this invention, the poisoning effect of the organomercaptan product can be minimized. As a result, both catalytic activity and selectivity increase substantially and high yields of organomercaptan product, e.g., in excess of 98%, can readily be achieved. The hydrogenolysis reaction herein has also been found to occur at more moderate temperatures and pressures. Low catalyst levels can be utilized and still provide completion in less than two hours with high conversion levels and excellent selectivity.
DESCRIPTION OF PREFERRED EMBODIMENTS The starting sulfide of the present invention can be chosen from among those of the general formula (I):
(I)
In sulfide (I), each R1 is the same or different alkyl group of up to about 6 carbon atoms and preferably of up to 4 carbon atoms, e.g., methyl, ethyl, propyl or butyl; aryl group of up to about 10 carbon atoms such as phenyl or naphthyl; alkoxy group of up to about 6 carbon atoms, and preferably up to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, or isobutoxy; or at least two of R1 and the silicon atom to which they are bonded form a ring system having up to about 12 ring members with no ethylenic unsaturation and optionally containing one or more oxygen, sulfur and/or nitrogen heteroatom members, e.g., the ring system having the structure
each R2 is a divalent hydrocarbon group containing no ethylenic unsaturation and having up to about 20 carbon atoms, and preferably up to about 12 carbon atoms, e.g., a linear or branched alkylene group such as methylene, ethylene, 1 ,2-propylene, 1,3-propylene, 2-methyl-l , 3- propylene, 3 methyl-1, 3-propylene, 3,3-dimethyl-l, 3-propylene, ethylidene or isopropylidene, a cycloalkylene group such as cyclohexylene or cycloheptylene, an arylene group such as phenylene, tolylene, xylylene or naphthylene, and m is 0 to 8 and preferably 0 to 4.
Reaction of sulfide (1) with hydrogen to provide organomercaptan product (II) in accordance with the invention can be thought of as proceeding in accordance with the reaction:
((Rl) _si_R2_s \_Sm + (m+1) H2 Cata,g^nin 2 (R>)3-Si-R2-SH + mH2S
Inhibiting agent
Many examples of sulfide (I) that can be used for preparing organomercaptans in accordance with the present invention and methods for their manufacture are known in the art and include those disclosed in, e.g., U.S. Patent Nos. 4,072,701 ; 4,408,064; 5,489,701 ;
5,466,848; 5,596,116; 5,663,395; 5,663,396; 5,859,275; 5,892,085; 6,147,241; 6,242,652; and,
6,274,755, the contents of which are incorporated by reference herein.
Examples of useful disilylalkyldisulfides of formula (I) include bis [3- (triethoxysilyl)propyl] disulfide [56706-10-6], bis[3-(trimethoxysilyl)propyl] disulfide [351 12-
74-4], 4, 13-diethoxy-4, 13-dimethyl-3, 14-dioxa-8, 9-dithia-4, 13-disilahexadecane [188561-27-
5], 4,4,13,13-tetraethoxy-6,l l-dimethyl-3,14-Dioxa-8,9-dithia-4,13-disilahexadecane [89552-
64-7], 8, l l-dimethyl-5, 5, 14, 14- tetrapropoxy-4, 15-dioxa-9, 10-dithia-5, 14-disilaoctadecane
[170573-44-1], 3, 3, 12, 12-tetramethoxy-6, 9-dimethyl-2, 13-dioxa-7, 8-dithia-3, 12-
disilatetradecane [170573-43-0], 3, 3, 12, 12-tetramethoxy-4, 11 -dimethyl-2, 13-dioxa-7, 8- dithia-3, 12-disilatetradecane [182814-38-6], 6, 13-dimethyl-5, 5, 14, 14-tetrapropoxy-4, 15- dioxa-9, 10-dithia-5, 14-disilaoctadecane [182814-43-3], bis[3-(tributoxysilyl)propyl] disulfide [42168-82-4] and 5, 14-diethyl-3, 16-dimethyl-5, 14-bis (l-methylpropoxy)-4, 15-dioxa-9, 10- dithia-5, 14-disilaoctadecane. [180003-88-7].
Examples of useful disilylalkyltrisulfides of formula (I) include bis [3-(triethoxysilyl) propyl] trisulfide [56706-11-7], bis [3-(trimethoxysilyl)proρyl] trisulfide [40550-17-2], bis[3- (triisopropoxysilyl)propyl] trisulfide [63501-63-3], 3, 13-dibutyl-3, 13-dimethoxy-2, 14-dioxa-7, 8, 9-trithia-3, 13-disilapentadecane [180003-90-1], 3-(tributoxysilyl)propyl 3-(trimethoxysilyl) propyl trisulfide [89552-63-6], (trithiodi-3, l-propanediyl)bis[tris(cyclopentyloxy)-silane
[180003-75-2] and 5, 21-diethyl-8, 8, 18, 18-tetrakis[(2-ethylhexyl)oxy]-7, 19-dioxa-12, 13, 14- trithia-8, 18-disilapentacosane [180003-70-7].
Examples of useful disilylalkyltetrasulfides of formula (I) include bis [3- (trimethoxysilyl)propyl] tetrasulfide [41453-78-5], (tetrathiodi-3, 1-propanediyl) bis[tris(isooctyloxy)-silane [180007-08-3], bis[3-triethoxysilyl)propyl] tetrasulfide [40372-72- 3], 4, 4-diethoxy-15, 15-bis (ethoxymethoxy)-3, 16, 18-trioxa-8, 9, 10, 1 l-tetrathia-4, 15- disilaeicosane [167216-77-5], 6, 6, 17, 17-tetrakis(ethoxymethoxy)-3, 5, 18, 20-tetraoxa-10, 11, 12, 13-tetrathia-6, 17-disiladocosane [203457-58-3], 1, 1 '-(tetrathiodi-3, 1 -propanediyl)bis-2, 8,9-trioxa-5-aza-l-silabicyclo [3.3.3]undecane [68704-61-0], bis[3-(diethoxymethylsilyl)propyl] tetrasulfide [70253-72-4], 2, 17-dimethyl-4, 4, 15, 15-tetrakis (l-methylethoxy)-3, 16-dioxa-8, 9, 10, 1 l-tetrathia-4, 15-disilaoctadecane [63501-62-2], 4, 4, 15, 15-tetraethoxy-7, 12-dimethyl-3, 16-dioxa-8, 9, 10, 1 l-tetrathia-4, 15-disilaoctadecane [57640-08-1], 5, 16, 16-triethoxy-5- methoxy-4, 17-dioxa-9, 10, 11, 12-tetrathia-5, 16-disilaheneicosane [180003-77-4], 6, 6, 17, 17- tetrabutoxy-5, 18-dioxa-10, 11, 12, 13-tetrathia-6, 17-disiladocosane [57640-06-9], 3, 3, 14, 14- tetramethoxy-5, 12-dimethyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane [180004- 00-6], 3, 14-bis(l,l-dimethylethyl)-3, 14-dimethoxy-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-
disilahexadecane [243458-27-7], disilatriacontane [57640-07-0], 10, 10, 21, 21- tetrakis(octyloxy)-9, 22-dioxa-14, 15, 16, 17-tetrathia-10, 21 -disilatriacontane [180003-68-3],
10, 21-diethoxy-10, 21-bis (octyloxy)-9, 22-dioxa-14, 15, 16, 17-tetrathia-10, 21- disilatriacontane [57640-13-8], 10, 10, 21-triethoxy-21-(octyloxy)-9, 22-dioxa-14, 15, 16, 17- tetrathia-10, 21 -disilatriacontane [57640-12-7], tetrathiodi-3, l-propanediyl)bis[tris
(cyclohexyloxy)-silane [180003-74-1], 3, 14-dimethoxy-3, 14-diphenyl-2, 15-dioxa-7, 8, 9, 10- tetrathia-3, 14-disilahexadecane [180003-91-2], 6, 17-diethoxy- 6, 17-diphenyl-5, 18-dioxa-10,
11, 12, 13-tetrathia-6, 17-disiladocosane [243458-31-3], 14-ethoxy-3, 3-dimethoxy-14-phenyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilanonadecane [180003-92-3] and 3,3, 14, 14- tetramethoxy-6, l l-diphenyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane [137264- 06-3].
It is well recognized that the known tetrasulfides are in fact average compositions, including a range from disulfide to octasulfide or higher, and typically are not pure tetrasulfides. Similarly, the useful disulfides and trisulfides can be provided as mixtures, the use of which is also contemplated herein.
The disilylalkyldisulfides are generally preferred due to generation of less by-product H2S, with the methoxy and ethoxydisilylpropyldi sulfides being more preferred.
Hydrogenolysis conditions can include a hydrogen pressure from about 100 psig to about 1000 psig and preferably from about 300 psig to about 600 psig, a temperature of from about 160°C to about 200°C and preferably from about 180°C to about 190°C, a reaction time from about 1 hour to about 5 hours and preferably from about 2 hours to about 3 hours.
The catalyst employed in the hydrogenolysis reaction is chosen from amongst the Group VIII metals and is preferably selected from the group consisting of nickel, cobalt, rhodium and ruthenium. The catalyst is preferably one that is supported on any one of numerous known and conventional catalyst support materials, e.g., diatomaceous earth, carbon, silica, alumina, aluminosilicate, and the like.
The amount of catalyst employed can vary widely provided of course, it is a catalytically effective amount. In general, catalyst levels of from about 0.1 wt. % to about 10 wt. % and preferably from about 0.5 wt. % to about 1 wt. % based on the weight of sulfide (I) reactant can be employed with good results. The catalyst poisoning inhibitory agent of the present can be selected to be water (except where the organomercaptan product contains one or more water sensitive silane groups); an alkanol of from 1 to 6 carbon atoms, preferably selected to match the alkoxy group(s) R2 of the sulfide (I) reactant, and preferably one selected from the group consisting of methanol, ethanol, butanol and isobutanol; and, hydrogen sulfide. Catalyst poisoning inhibitory amounts of the catalyst poisoning inhibitory agent can vary widely and in most cases can be present in the reaction medium at a level of from about 5 wt. % to about 50 wt. % and preferably from about 5 wt. % to about 20 wt. % based on the weight of sulfide (I).
Comparative Examples 1 -6 illustrate a catalyzed process for making organomercaptan which omits the use of a catalyst poisoning inhibitory agent and as such, are outside the scope of the present invention. Examples 1-27 are illustrative of the process for preparing organomercaptan of the present invention and clearly demonstrate the advantage of using a catalyst poisoning inhibitory agent. In the tables of data which accompany all of the examples, the following terms have the designated meanings:
"Mercaptan": 3-mercaptopropyltriethoxysilane "Monosulfide": bis(3-(triethoxysilylpropyl) sulfide
"Disulfide": bis(3-triethoxysilylpropyl) disulfide
"Polysulfide": mixtures of bis[3-(triethoxysilyl)propyl] trisulfide and higher sulfides
Comparative Example 1 In a 1 liter Hastelloy C autoclave equipped with a mechanical stirrer, cooling coils and a thermocouple, 591.4 grams of mainly bis(3-triethoxysilylypropyl) disulfide were combined with 2.0 grams of a 55 wt % nickel catalyst on a kieselguhr support. After purging the autoclave with nitrogen and then hydrogen, the reactor was pressurized to 620 psig with hydrogen and heated to 190°C while stirring at 1022 rpm. After approximately 180 minutes, the reaction mass was cooled to room temperature and vented to atmospheric pressure. The contents of the reactor were sampled and analyzed by gas ckromatography with the following results:
Table 1
Comparative Examples 2-6 Employing substantially the same procedure as described in Comparative Example 1 , additional reactions were carried out with the conditions and results as set forth in Table 2 below.
Table 2
Example 1
In a 1 liter Hastelloy C autoclave equipped with a mechanical stirrer, cooling coils and a thermocouple, 360.2 grams of mainly bis(3-triethoxysilylypropyl) disulfide were combined with 40.7 grams ethanol and 2.0 grams of a 55 wt % nickel catalyst on a kieselguhr support. After purging the autoclave with nitrogen and then hydrogen, the reactor was pressurized to 624 psig with hydrogen and heated to 190°C while stirring at 1007 rpm. After approximately 180 minutes, the reaction mass was cooled to room temperature and vented to atmospheric pressure. The contents of the reactor were sampled and analyzed by gas chromatography with the following results:
Table 3
Example 2 In a 1 liter Hastelloy C autoclave equipped with a mechanical stirrer, cooling coils and a thermocouple, 310.3 grams of mainly bis(3-triethoxysilylypropyl) disulfide were combined with 5.0 grams of a 55 wt % nickel catalyst on a kieselguhr support. After purging the autoclave with nitrogen and then hydrogen, the reactor was charged with 35 grams of hydrogen sulfide, pressurized to 615 psig with hydrogen and heated to 190°C while stirring at 1087 rpm. After approximately 150 minutes, the reaction mass was cooled to room temperature and vented to atmospheric pressure. The contents of the reactor were sampled and analyzed by gas chromatography with the following results:
Table 4
Examples 3-25 Employing substantially the same procedures as described in Examples 1-3, additional reactions were carried out employing ethanol as the catalyst poisoning inhibitory agent with the conditions and results as set forth in Table 5 below:
Table 5
Claims
1. Process for preparing an organomercaptan which comprises reacting a sulfide of the general formula (I)
(V)3— Si— R2-s)-Sm 2 (I) in which each R1 is the same or different alkyl group of up to 6 carbon atoms, aryl group of up to 10 carbon atoms or alkoxy group of up to 6 carbon atoms, or at least two of R1 and the silicon atom to which they are bonded form a ring system having up to 12 ring members with no ethylenic unsaturation and optionally containing one or more heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, each R is the same or different divalent hydrocarbon group containing no ethylenic unsaturation and having up to 20 carbon atoms and m is 0 to 8, with hydrogen under hydrogenolysis conditions in the presence of a catalytically effective amount of Group VIII metal catalyst and in the presence of a catalyst poisoning inhibiting amount of a catalyst poisoning inhibitory agent selected from the group consisting of water, except where the mercaptan product contains at least one hydrolyzable silane group, alkanol of from 1 to 6 carbon atoms, hydrogen sulfide and mixtures thereof to provide organomercaptan product of the general formula (II) (R')3-Si-R2-SH (II) in which R1 and R2 each has one of the aforestated meanings.
2. The process of Claim 1 wherein at least one R1 is an alkyl group selected from the group consisting of methyl, ethyl, propyl and butyl and wherein each R2 is the same or different divalent alkylene radical of up to 12 carbon atoms.
3. The process of Claim 1 wherein at least one R1 is a phenyl group and wherein each R2 is the same or different divalent alkylene radical of up to 12 carbon atoms.
4. The process of Claim 1 wherein at least one R1 is an alkoxy group selected from the group consisting of methoxy, ethoxy, propoxy or butoxy and wherein each R2 is the same or different divalent alkylene radical of up to 12 carbon atoms.
5. The process of Claim 1 wherein sulfide (I) is a disilylalkyldisulfide selected from the group consisting of bis [3-(triethoxysilyl)propyl] disulfide, bis[3- (trimethoxysilyl)propyl] disulfide, 4, 13-diethoxy-4, 13-dimethyl-3, 14-dioxa-8, 9-dithia-4, 13- disilahexadecane, 4, 4, 13, 13-tetraethoxy-3, 14-dioxa-8, 9-dithia-4, 13-disilahexadecane, 8, 1 1- dimethyl-5, 5, 14, 14- tetrapropoxy-4, 15-dioxa-9, 10-dithia-5, 14-disilaoctadecane, 3, 3, 12, 12- tetramethoxy-6, 9-dimethyl-2, 13-dioxa-7, 8-dithia-3, 12-disilatetradecane, 3, 3, 12, 12- tetramethoxy-4, l l-dimethyl-2, 13-dioxa-7, 8-dithia-3, 12-disilatetradecane, 6, 13-dimethyl-5, 5, 14, 14-tetrapropoxy-4, 15-dioxa-9, 10-dithia-5, 14-disilaoctadecane, bis[3- (tributoxysilyl)propyl] disulfide and 5, 14-diethyl-3, 16-dimethyl-5, 14-bis (l-methylpropoxy)-4, 15-dioxa-9, 10-dithia-5, 14-disilaoctadecane.
6. The process of Claim 1 wherein sulfide (I) is a disilylalkyltrisulfide selected from the group consisting of bis [3-(triethoxysilyl)propyl] trisulfide, bis [3-(trimethoxysilyl)propyl] trisulfide, bis[3-(triisopropoxysilyl)propyl] trisulfide, 3, 13-dibutyl-3, 13-dimethoxy-2, 14- dioxa-7, 8, 9-trithia-3, 13-disilapentadecane, 3-(tributoxysilyl)propyl 3-(trimethoxysilyl)propyl trisulfide, (trithiodi-3, 1-propanediyl) bis[tris(cyclopentyloxy)-silane and 5, 21-diethyl-8, 8, 18, 18-tetrakis[(2-ethylhexyl)oxy]-7, 19-dioxa-12, 13, 14-trithia-8, 18-disilapentacosane.
7. The process of Claim 1 wherein sulfide (I) is a disilylalkyltetrasulfide selected from the group consisting of bis [3-(trimethoxysilyl)propyl] tetrasulfide, (tetrathiodi-3, l-propanediyl)bis[tris(isooctyloxy)-silane, bis[3-triethoxysilyl)propyl] tetrasulfide, 4, 4- diethoxy-15, 15-bis (ethoxymethoxy)-3, 16, 18-trioxa-8, 9, 10, 1 l-tetrathia-4, 15-disilaeicosane, 6, 6, 17, 17-tetrakis(ethoxymethoxy)-3, 5, 18, 20-tetraoxa-10, 11, 12, 13-tetrathia-6, 17- disiladocosane, 1, T-(tetrathiodi-3, l-propanediyl)bis-2, 8,9-trioxa-5-aza-l-silabicyclo [3.3.3]undecane, bis [3-(diethoxymethylsilyl)propyl] tetrasulfide, 2, 17-dimethyl-4, 4, 15, 15- tetrakis (l-methylethoxy)-3, 16-dioxa-8, 9, 10, 1 l-tetrathia-4, 15-disilaoctadecane, 4, 4, 15, 15- tetraethoxy-7, 12-dimethyl-3, 16-dioxa-8, 9, 10, 1 1 -tetrathia-4, 15-disilaoctadecane, 5, 16, 16- triethoxy-5-methoxy-4, 17-dioxa-9, 10, 11, 12-tetrathia-5, 16-disilaheneicosane, 6, 6, 17, 17- tetrabutoxy-5, 18-dioxa-lO, 11 , 12, 13-tetrathia-6, 17-disiladocosane, 3, 3, 14, 14-tetramethoxy- 5, 12-dimethyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane, 3, 14-bis(l,l- dimethylethyl)-3, 14-dimethoxy-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane, disilatriacontane, 10, 10, 21, 21-tetrakis(octyloxy)-9, 22-dioxa-14, 15, 16, 17-tetrathia-10, 21- disilatriacontane, 10, 21 -diethoxy- 10, 21 -bis (octyloxy)-9, 22-dioxa-14, 15, 16, 17-tetrathia- 10, 21 -disilatriacontane, 10, 10, 21-triethoxy-21-(octyloxy)-9, 22-dioxa-14, 15, 16, 17-tetrathia- 10, 21 -disilatriacontane, tetrathiodi-3, l-propanediyl)bis[tris(cyclohexyloxy)-silane, 3, 14- dimethoxy-3, 14-diphenyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane, 6, 17- diethoxy- 6, 17-diphenyl-5, 18-dioxa-lO, 1 1, 12, 13-tetrathia-6, 17-disiladocosane, 14-ethoxy-3, 3-dimethoxy-14-phenyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilanonadecane and 3,3, 14, 14- tetramethoxy-6, l l-diphenyl-2, 15-dioxa-7, 8, 9, 10-tetrathia-3, 14-disilahexadecane.
8. The process of Claim 1 wherein the hydrogenolysis conditions include a hydrogen pressure of from 300 psig to 600 psig, a temperature of from 160°C to 190°C and a reaction time of from 2 hours to 5 hours.
9. The process of Claim 1 wherein the catalyst is present at from 1 to 10 weight percent by weight of sulfide (I).
10. The process of Claim 1 wherein the catalyst poisoning inhibitory agent is present in an amount of from 5 to 50 weight percent by weight of sulfide (I).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BRPI0214066-7A BR0214066B1 (en) | 2001-11-05 | 2002-10-11 | process for the preparation of silylorganomercaptans. |
| DE60219193T DE60219193T2 (en) | 2001-11-05 | 2002-10-11 | PROCESS FOR THE PREPARATION OF SILYLORGANOMERCAPTANES |
| JP2003542198A JP4632663B2 (en) | 2001-11-05 | 2002-10-11 | Method for producing silylorganomercaptan |
| EP02769065A EP1448570B1 (en) | 2001-11-05 | 2002-10-11 | Process for preparing silylorganomercaptans |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/012,286 | 2001-11-05 | ||
| US10/012,286 US6433206B1 (en) | 2001-11-05 | 2001-11-05 | Process for preparing silylorganomercaptans |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003040153A1 true WO2003040153A1 (en) | 2003-05-15 |
Family
ID=21754241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2002/032608 WO2003040153A1 (en) | 2001-11-05 | 2002-10-11 | Process for preparing silylorganomercaptans |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6433206B1 (en) |
| EP (1) | EP1448570B1 (en) |
| JP (1) | JP4632663B2 (en) |
| KR (1) | KR100940408B1 (en) |
| CN (1) | CN1280294C (en) |
| BR (1) | BR0214066B1 (en) |
| DE (1) | DE60219193T2 (en) |
| WO (1) | WO2003040153A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077008A (en) * | 2004-09-07 | 2006-03-23 | Degussa Ag | Method for producing mercaptorganyl(alkoxysilane) |
| JP2006077009A (en) * | 2004-09-07 | 2006-03-23 | Degussa Ag | Method for producing mercaptorganyl(alkoxysilane) |
| CN101616923B (en) * | 2007-01-05 | 2012-12-12 | 道康宁东丽株式会社 | Bis[tri(hydroxypolyalkyleneoxy)silylalkyl]polysulfide, method of manufacturing bis[tri(hydroxypolyalkyleneoxy)silylalkyl]polysulfide, tire rubber additive, and tire rubber composition |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6433206B1 (en) * | 2001-11-05 | 2002-08-13 | Crompton Corporation | Process for preparing silylorganomercaptans |
| DE102004030737A1 (en) * | 2004-06-25 | 2006-01-12 | Degussa Ag | Method and device for extracting substances from silane-modified fillers |
| DE102005020535B3 (en) * | 2005-05-03 | 2006-06-08 | Degussa Ag | Preparation of mercapto organyl(alkoxysilane) comprises reaction of bis(alkoxysilylorganyl)polysulfide with hydrogen in the presence of an alcohol and a doped metal catalyst (containing e.g. (iron) compound and a doping component) |
| DE102005038791A1 (en) * | 2005-08-17 | 2007-02-22 | Degussa Ag | New organosilicon compounds based on triethanolamine, useful as components of rubber mixtures for making e.g. tires, tubes and cable coatings |
| WO2007060934A1 (en) * | 2005-11-25 | 2007-05-31 | Bridgestone Corporation | Organosilicon compounds and rubber compositions made by using the same |
| DE102005060122A1 (en) * | 2005-12-16 | 2007-06-21 | Degussa Gmbh | Process for the preparation of (mercaptoorganyl) alkyl polyether silanes |
| DE102006004062A1 (en) | 2006-01-28 | 2007-08-09 | Degussa Gmbh | rubber compounds |
| DE102006027235A1 (en) * | 2006-06-09 | 2008-01-17 | Evonik Degussa Gmbh | rubber compounds |
| JP2008060117A (en) * | 2006-08-29 | 2008-03-13 | Konica Minolta Holdings Inc | Organic thin-film transistor and manufacturing method thereof |
| DE102008054967A1 (en) | 2008-12-19 | 2010-06-24 | Evonik Degussa Gmbh | Silatran-containing particles |
| CN106914146B (en) * | 2017-03-14 | 2019-05-28 | 常州大学 | A kind of thiolated modified TRIES seperation film and its preparation method and application |
| CN110621732B (en) * | 2017-05-12 | 2022-01-07 | 朗盛德国有限责任公司 | Rubber mixtures containing sulfur-containing organosilicon compounds |
| DE102017221269A1 (en) * | 2017-11-28 | 2019-05-29 | Evonik Degussa Gmbh | Silane mixtures and process for their preparation |
| US11208518B2 (en) | 2018-12-11 | 2021-12-28 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
| US10947380B2 (en) | 2018-12-20 | 2021-03-16 | The Goodyear Tire & Rubber Company | Functionalized polymer, rubber composition and pneumatic tire |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336386A (en) * | 1963-03-12 | 1967-08-15 | Uniroyal Inc | Hydrogenation with platinum metal sulfide catalyst |
| DE1903968A1 (en) * | 1969-01-28 | 1970-08-27 | Bayer Ag | Thiophenols with the sulphides or polysul- - phides of cobalt and nickel as catalyst from |
| GB1205537A (en) * | 1968-05-11 | 1970-09-16 | Bayer Ag | A process for the production of thiophenols |
| US5493058A (en) * | 1993-10-20 | 1996-02-20 | Elf Aquitaine Production | Synthesis of methyl mercaptan from dimethyl disulphide |
| US6147242A (en) * | 1998-12-28 | 2000-11-14 | Degussa-Huls Ag | Method of producing silylalkylthiols |
| US6433206B1 (en) * | 2001-11-05 | 2002-08-13 | Crompton Corporation | Process for preparing silylorganomercaptans |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1054032A (en) * | 1962-06-30 | 1900-01-01 | ||
| NL302825A (en) * | 1962-12-31 | 1900-01-01 | ||
| US3957844A (en) * | 1972-08-14 | 1976-05-18 | Union Carbide Corporation | Process for making mercapto substituted silicon compounds |
| DE2542534C3 (en) | 1975-09-24 | 1979-08-02 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the preparation of sulfur-containing organosilicon compounds |
| DE2856229A1 (en) | 1978-12-27 | 1980-07-03 | Degussa | BIS- (SILYLAETHYL) -OLIGOSULFIDES AND METHOD FOR THE PRODUCTION THEREOF |
| JPS5970692A (en) * | 1982-10-16 | 1984-04-21 | Sanwa Kagaku Kenkyusho:Kk | Novel organic silicon compound, its non-toxic salt, its preparation and antitumor agent containing said compound as active component |
| EP0134200B1 (en) * | 1983-08-12 | 1987-03-04 | Ciba-Geigy Ag | Process for the preparation of mercaptans |
| US5489701A (en) | 1994-09-28 | 1996-02-06 | Osi Specialties, Inc. | Process for the preparation of silane polysulfides |
| US5466848A (en) | 1994-09-28 | 1995-11-14 | Osi Specialties, Inc. | Process for the preparation of silane polysulfides |
| US5596116A (en) | 1995-09-11 | 1997-01-21 | Osi Specialties, Inc. | Process for the preparation of silane polysulfides |
| DE19541404A1 (en) | 1995-11-07 | 1997-05-15 | Degussa | Process for the selective synthesis of silylalkyl disulfides |
| US5728887A (en) * | 1996-04-10 | 1998-03-17 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenolysis of organic thiocyanates and disulfides to thiols |
| US5663396A (en) | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
| DE19651849A1 (en) | 1996-12-13 | 1998-06-18 | Degussa | Process for the preparation of bis (silylorganyl) polysulfanes |
| DE19734295C1 (en) | 1997-08-08 | 1999-02-25 | Degussa | Process for the production of high purity organosilicon disulfanes |
| DE19750503A1 (en) * | 1997-11-14 | 1999-05-20 | Degussa | Bis-(silylorganyl)polysulfides for enhancing effectiveness of rubber-vulcanizing compounds |
| JP3498559B2 (en) * | 1997-12-01 | 2004-02-16 | 信越化学工業株式会社 | Method for producing short-chain polysulfide silane mixture |
| DE19848482C1 (en) | 1998-10-21 | 2000-06-08 | Degussa | Process for the preparation of organosilicon disulfanes |
| DE19857223C5 (en) * | 1998-12-11 | 2010-02-04 | Evonik Degussa Gmbh | Process for the preparation of propyl silanes |
| DE19930495C1 (en) | 1999-07-01 | 2000-11-09 | Degussa | Alkoxysilylalkylpolysulfide compounds, useful assistants in the production of silica filled rubber, made by reacting silyl alkyl halides with alkali polysulfides obtained by reacting alkali hydroxides with sulfur in non-aqueous solvent |
| US6242652B1 (en) | 2000-03-03 | 2001-06-05 | Phillips Petroleum Company | Process for producing organic trisulfides |
-
2001
- 2001-11-05 US US10/012,286 patent/US6433206B1/en not_active Expired - Lifetime
-
2002
- 2002-10-11 KR KR1020047006884A patent/KR100940408B1/en active IP Right Grant
- 2002-10-11 EP EP02769065A patent/EP1448570B1/en not_active Expired - Lifetime
- 2002-10-11 CN CNB028255143A patent/CN1280294C/en not_active Expired - Fee Related
- 2002-10-11 JP JP2003542198A patent/JP4632663B2/en not_active Expired - Fee Related
- 2002-10-11 WO PCT/US2002/032608 patent/WO2003040153A1/en active IP Right Grant
- 2002-10-11 BR BRPI0214066-7A patent/BR0214066B1/en not_active IP Right Cessation
- 2002-10-11 DE DE60219193T patent/DE60219193T2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336386A (en) * | 1963-03-12 | 1967-08-15 | Uniroyal Inc | Hydrogenation with platinum metal sulfide catalyst |
| GB1205537A (en) * | 1968-05-11 | 1970-09-16 | Bayer Ag | A process for the production of thiophenols |
| DE1903968A1 (en) * | 1969-01-28 | 1970-08-27 | Bayer Ag | Thiophenols with the sulphides or polysul- - phides of cobalt and nickel as catalyst from |
| US5493058A (en) * | 1993-10-20 | 1996-02-20 | Elf Aquitaine Production | Synthesis of methyl mercaptan from dimethyl disulphide |
| US6147242A (en) * | 1998-12-28 | 2000-11-14 | Degussa-Huls Ag | Method of producing silylalkylthiols |
| US6433206B1 (en) * | 2001-11-05 | 2002-08-13 | Crompton Corporation | Process for preparing silylorganomercaptans |
Non-Patent Citations (6)
| Title |
|---|
| BERGMANN M ET AL: "Katalytische Hydrierung von l-Cystin zu l-Cystein - Catalytic hydrogenation of l-cystine to l-cysteine", BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, VERLAG CHEMIE, WEINHEIM, DE, vol. 63, 1930, pages 987 - 989, XP002220429 * |
| CALAIS C ET AL: "Selective reduction of diphenyldisulphides catalysed by sulphides - influence of the nature of the catalyst", JOURNAL OF CATALYSIS, vol. 144, 1993, pages 160 - 174, XP002227637, ISSN: 0021-9517 * |
| ITABASHI K: "Pressure hydrogenation of organic compounds by molybdenum sulphide catalyst. VI. Reduction of dithioglycolic acid", YUKI GOSEI KAGAKU KYOKAI SHI - JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, vol. 18, 1960, pages 347 - 351, XP009003503, ISSN: 0037-9980 * |
| ITABASHI K: "Pressure hydrogenation of organic compounds by molybdenum sulphide catalyst. VIII. Synthesis of n-dodecylmercaptan from d-n-dodecyl disulphide by reduction", YUKI GOSEI KAGAKU KYOKAI SHI - JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, vol. 18, 1960, pages 480 - 484, XP009003504, ISSN: 0037-9980 * |
| ITABASHI K: "Pressure hydrogenation of organic cpds by molybdenum sulphide catalyst. IV. Reduction of sulphides", YUKI GOSEI KAGAKU KYOKAI SHI - JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY, vol. 17, 1959, pages 611 - 616, XP009003502, ISSN: 0037-9980 * |
| SMITH BROADMENT H ET AL: "Rhenium sulphides as liquid-phse hydrogenation catalysts. A comparison with molybdenum sulphide and cobalt polysulphide", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 76, 20 March 1954 (1954-03-20), pages 1519 - 1523, XP002227638, ISSN: 0002-7863 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006077008A (en) * | 2004-09-07 | 2006-03-23 | Degussa Ag | Method for producing mercaptorganyl(alkoxysilane) |
| JP2006077009A (en) * | 2004-09-07 | 2006-03-23 | Degussa Ag | Method for producing mercaptorganyl(alkoxysilane) |
| CN101616923B (en) * | 2007-01-05 | 2012-12-12 | 道康宁东丽株式会社 | Bis[tri(hydroxypolyalkyleneoxy)silylalkyl]polysulfide, method of manufacturing bis[tri(hydroxypolyalkyleneoxy)silylalkyl]polysulfide, tire rubber additive, and tire rubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60219193D1 (en) | 2007-05-10 |
| CN1280294C (en) | 2006-10-18 |
| JP4632663B2 (en) | 2011-02-16 |
| CN1612883A (en) | 2005-05-04 |
| EP1448570B1 (en) | 2007-03-28 |
| EP1448570A1 (en) | 2004-08-25 |
| DE60219193T2 (en) | 2007-08-23 |
| KR20050035179A (en) | 2005-04-15 |
| BR0214066A (en) | 2004-10-13 |
| BR0214066B1 (en) | 2012-11-27 |
| KR100940408B1 (en) | 2010-02-02 |
| JP2005510520A (en) | 2005-04-21 |
| US6433206B1 (en) | 2002-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6433206B1 (en) | Process for preparing silylorganomercaptans | |
| KR102201058B1 (en) | Organoaminosilanes and methods for making same | |
| US4503160A (en) | Hydrosilylation method, catalyst and method for making | |
| KR101184481B1 (en) | Process for Producing MercaptoorganylAlkoxysilane | |
| US7005532B2 (en) | Process of producing alkoxysilanes | |
| US6417381B1 (en) | Process for preparing bis(silylorgano)amines | |
| US6388119B1 (en) | Preparation of organosilanes | |
| EP3071584A1 (en) | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation | |
| EP1754708B1 (en) | Preparation of 1-(alkoxysilyl) ethyl-1,1,3,3-tetramethyldisiloxane | |
| KR101281245B1 (en) | Process for preparing mercapto-organyl(alkoxysilanes) | |
| US6242627B1 (en) | Process for preparing primary aminoorganosilanes | |
| KR100818835B1 (en) | Preparation of Secondary Aminoisobutylalkoxysilanes | |
| US4533744A (en) | Hydrosilylation method, catalyst and method for making | |
| JP4130489B2 (en) | Hydrosilylation of alkynes using cycloalkenes as catalyst modifiers. | |
| CN113399001A (en) | Catalyst for olefin hydrosilylation reaction, preparation method and application thereof | |
| JPH02300192A (en) | Production of 3-(n-(2-aminoethyl))aminopropylalkoxysilane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR CA CN JP KR |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR |
|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 2003542198 Country of ref document: JP Ref document number: 1020047006884 Country of ref document: KR |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2002769065 Country of ref document: EP |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 20028255143 Country of ref document: CN |
|
| WWP | Wipo information: published in national office |
Ref document number: 2002769065 Country of ref document: EP |
|
| WWG | Wipo information: grant in national office |
Ref document number: 2002769065 Country of ref document: EP |